CN106696115A - Preparation method for AES resin - Google Patents

Preparation method for AES resin Download PDF

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Publication number
CN106696115A
CN106696115A CN201611156731.0A CN201611156731A CN106696115A CN 106696115 A CN106696115 A CN 106696115A CN 201611156731 A CN201611156731 A CN 201611156731A CN 106696115 A CN106696115 A CN 106696115A
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CN
China
Prior art keywords
aes
preparation
san
resin
grafted copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611156731.0A
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Chinese (zh)
Inventor
刘秋丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Gaohua Zhiben Chemical Technology Co Ltd
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Shaanxi Gaohua Zhiben Chemical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Gaohua Zhiben Chemical Technology Co Ltd filed Critical Shaanxi Gaohua Zhiben Chemical Technology Co Ltd
Priority to CN201611156731.0A priority Critical patent/CN106696115A/en
Publication of CN106696115A publication Critical patent/CN106696115A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C2045/0096—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor drying the moulding material before injection, e.g. by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76531—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a preparation method for AES resin and belongs to the field of material preparation. The preparation method for the AES resin is characterized by comprising the following steps that firstly, an AES grafted copolymer is cut into pieces, a solvent is removed in a vacuum drying box till the constant weight is achieved, and SAN resin is dried in an oven, the AES grafted copolymer and the SAN resin are put into a high-speed stirring machine and mixed to be uniform; secondly, extruding and prilling are carried out through a double-helix extruder; thirdly, an injection molding machine is used for carrying out forming; and fourthly, an AES resin sheet is subjected to cold pressing for 5 min and is taken out to be cut into needed size through a sheet cutter, and preparation is completed. By means of improvement of an existing process, the AES grafted copolymer is prepared through a solution method, and AES resin is obtained through commixing of the AES grafted copolymer and the SAN. Along with increase of the amount of the AES grafted copolymer, the SAN fusing time is shortened, and the processing torque of the material is improved.

Description

A kind of preparation method of AES resins
Technical field
The invention belongs to field of material preparation, more particularly to a kind of preparation method of AES resins.
Background technology
AES resins are also referred to as EPSAN resins, are the copolymers of ethylene propylene diene rubber graft phenylethene, acrylonitrile.Rubber phase Using the fabulous ethylene propylene diene rubber of weatherability, assign AES resins excellent ageing-resistant performance, even if for a long time exposed to outdoor Ultraviolet irradiates, and rainforest is uncoated under the conditions of light and ozone that performance can also be kept constant, is widely used in outdoor products.AES Resin not only has excellent ageing-resistant performance, because rubber phase EPDM glass transition temperatures are low, makes the low-temperature impact-resistant of AES Performance is better than ABS, AAS, therefore, the long service lifes such as auto parts machinery, billboard are more and more applied to, it is safe and reliable Field.Need not take steps to slow down its it is aging make it in price, it is more competitive in use time.
AES naval stores is graininess, and milky is nontoxic, tasteless.With excellent impact resistance, low temperature usability, The performances such as coloring, oil resistivity, insulating properties, its weatherability is 4-8 times of ABS resin, processing characteristics, surface gloss and ABS Resin is similar, and ABS resin can be replaced to be used in some weatherabilities requirement field high.
AES resins are the products being blended by two kinds of materials, and the cohesive force of two-phase interface determines the quality of material property. The formation of Blending Processes median surface layer can be divided into two steps：First, two-phase contacts with each other, right latter two high molecular polymer Phase counterdiffusion between chain.In two kinds of interactive interface layer, one is double-component chemical bond linkage, such as graft copolymer and embedding Section copolymer；Equations of The Second Kind is combined by Van der Waals force, and graft copolymer and block copolymer there is also Van der Waals force, so this Existing chemical bond in compound boundary layer of birdsing of the same feather flock together has Van der Waals force again.Interfacial tension, boundary can be produced between two components for contacting with each other Face tension force is smaller, and its bond strength is bigger.
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of preparation method of AES resins.
The technical scheme is that：
A kind of preparation method of AES resins, it is characterised in that comprise the following steps：（1）AES graft copolymers are shredded and is taking out true To constant weight, SAN resins are dried desolventizing in an oven, and EBS is plasticizer, and its consumption accounts for AES graft copolymers in empty drying box With the 5% of SAN resin qualities, raw material is well mixed in being put into homogenizer；（2）Then extruded by Twin screw extruder and made Grain, particle dries 12h in 40 DEG C of baking ovens；（3）It is molded with injection machine；Vulcanizing press is warmed up to 175 DEG C, by lower good piece AES resin sheets are put into mould, it is ensured that full of mould, mold thickness 4mm preheats 10min, is forced into 150x105Pa, pressurize 5min；（4）Then the 5min that colds pressing takes out, and being cut into slitter needs size, completes to prepare.
The preparation method of AES resins of the present invention, the temperature of the Twin screw extruder is 140-170 DEG C.
The preparation method of AES resins of the present invention, the engine speed of the Twin screw extruder is 80rpm.
The preparation method of AES resins of the present invention, the temperature of the injection machine is 33-190 DEG C.
The preparation method of AES resins of the present invention, the injection pressure of the injection machine is 60bar.
The preparation method of AES resins of the present invention, the cool time of the injection machine is 5s.
The technical effects of the invention are that：
The preparation method of AES resins of the present invention, by the improvement to existing process, prepares AES and is grafted using solwution method Copolymer, AES graft copolymers are obtained AES resins with SAN blendings.With increasing for AES graft copolymer consumptions, when SAN is melted Between shorten, the increase of the processing moment of torsion of material；Impact strength slowly increases when rubber content is less than 10%, and brittle-ductile transition occurs in rubber Glue phase content 15%~20%；At 1%, AES resin impact strengths reach maximum to TDDM consumptions；Increase with rubber phase consumption, The resin stretched intensity of AES diminishes, elongation at break increase.
Specific embodiment
Embodiment
A kind of preparation method of AES resins, it is characterised in that comprise the following steps：（1）AES graft copolymers are shredded Desolventizing to constant weight is vacuumized in drying box, SAN resins are dried in an oven, and EBS is plasticizer, and its consumption accounts for AES grafting altogether The 5% of polymers and SAN resin qualities, raw material is well mixed in being put into homogenizer；（2）Then squeezed by Twin screw extruder Go out granulation, particle dries 12h in 40 DEG C of baking ovens；（3）It is molded with injection machine；Vulcanizing press is warmed up to 175 DEG C, will be lower good The AES resin sheets of piece are put into mould, it is ensured that full of mould, and mold thickness 4mm preheats 10min, is forced into 150x105Pa, Pressurize 5min；（4）Then the 5min that colds pressing takes out, and being cut into slitter needs size, completes to prepare.
The preparation method of AES resins of the present invention, the temperature of the Twin screw extruder is 140 DEG C.
The preparation method of AES resins of the present invention, the engine speed of the Twin screw extruder is 80rpm.
The preparation method of AES resins of the present invention, the temperature of the injection machine is 33-190 DEG C.
The preparation method of AES resins of the present invention, the injection pressure of the injection machine is 60bar.
The preparation method of AES resins of the present invention, the cool time of the injection machine is 5s.Impact strength is to weigh The important indicator of AES resins, it is exactly in order that rubber can be uniform in SAN resins that graft modification is carried out to ethylene propylene diene rubber Dispersion, two-phase is reached compatibility well.Stress concentration center is played a part of in EPDM dispersions in the plastic, is subject to The effect of external force can induce a large amount of crazings and shear band, big energy be absorbed, so as to play a part of toughness reinforcing SAN resins.Rubber Glue mutually in the plastic can well under dispersion condition, and with the increase of rubber phase, the particle diameter of rubber phase can increase in system, rubber The increase of phase can bring difficulty to processing simultaneously, cause melt viscosity high, need to increase injection doses in injection moulding process.
Use grafting rate for 25% EPDM3960Q graft copolymers, rubber-phase content is 20%, by with SAN resins Blending prepares the AES resins of different rubber contents, while comparing research rubber-phase content to AES resins using surname rubber is not changed The influence of impact strength.Pure SAN resins impact strength 2KJ/m2, when rubber-phase content is less than 10%, with the increase of rubber phase, AES resin impact strengths are slowly increased；During rubber-phase content 8%, impact strength only has 4.2KJ/m2, 1 is increased compared with pure SAN Times；10%~20%, impact strength increases to be accelerated rubber-phase content, and impact strength is by 5.2 KJ/m2Rise to 15.4 KJ/ m2, impact strength improves 7.7 times compared with pure SAN.EP rubbers without it is modified directly with SAN resin alloys, with rubber The increase of glue phase, impact strength is big without substantially change, substantially without toughening effect.
EPDM rubber particle plays two important function in toughened system, and one is to induce a large amount of as stress concentration center Crazing and shear band, two is the development for controlling crazing, and terminates crazing, and will not develop into destructive crackle, crazing tip Stress field can induce the generation of shear band, and shear band can also prevent the product of the further development of crazing, crazing and shear band Raw and development will consume substantial amounts of energy, thus significantly improve material impact intensity.
With the increase of rubber phase, the resin stretched intensity of AES is gradually reduced, and elongation at break gradually increases.Rubber mutually increases, The hardness of material can be gradually reduced, and the crazing quantity produced by action of pulling stress will increase, and reach identical strain required Stress will reduce.
The consumption influence styrene of molecular weight regulator, acrylonitrile compolymer reaction, make to be grafted to the SAN molecular weight on EPDM Reduce, while free SAN molecular resins amount reduces, so as to produce influence to impact strength.Rubber-phase content in AES resins Rubber and plastic compares 20 when prepared by 20%, AES graft copolymer：80.Change molecular weight regulator consumption, prepare multigroup AES graft copolymerizations Thing, with the granulation of certain proportion SAN resin alloys, is made standard batten, determines its impact strength, and measure is extracted dividing for SAN Son amount, molecular weight regulator has a significant impact to free SAN molecular weight, because TDDM is chain-transferring agent, can induce chain tra nsfer, Reduce molecular weight of product.After adding TDDM in experiment, the grafting rate of EPDM is reduced, reduce EPDM top layers graft SAN amount.With The difference of molecular weight regulator consumption, at 1%, impact strength reaches peak value to consumption, be grafted to SAN molecular weight on EPDM with TDDM consumptions are inversely proportional, and optimum value is reached when TDDM consumptions are 1%.
TDDM can effectively adjust AES molecular resin amounts, and its chemical property is very active, it is easy to Large molecule active chain There is chain transfer reaction in free radical, living chain is lost activity and itself generate new free radical, this new freedom again simultaneously Base continues to trigger polymerization 16511.MFR is bigger, and the mobility of material is better, and same type of material molecular weight is lower.With TDDM consumptions Increase, the melt flow rate (MFR) of AES resins constantly increases, and relative molecular mass is constantly reduced.When TDDM mass fractions exceed When 0.4%, AES resin Ms FR improves notable.With increasing for AES graft copolymer consumptions, the SAN melting times shorten, material plus Work moment of torsion increases.

Claims (6)

1. a kind of preparation method of AES resins, it is characterised in that comprise the following steps：（1）AES graft copolymers are shredded and is being taken out To constant weight, SAN resins are dried desolventizing in an oven, and EBS is plasticizer, and its consumption accounts for AES graft copolymerizations in vacuum drying chamber The 5% of thing and SAN resin qualities, raw material is well mixed in being put into homogenizer；（2）Then extruded by Twin screw extruder Granulation, particle dries 12h in 40 DEG C of baking ovens；（3）It is molded with injection machine；Vulcanizing press is warmed up to 175 DEG C, by lower good piece AES resin sheets be put into mould, it is ensured that full of mould, mold thickness 4mm preheats 10min, is forced into 150x105Pa, protects Pressure 5min；（4）Then the 5min that colds pressing takes out, and being cut into slitter needs size, completes to prepare.
2. the preparation method of AES resins according to claim 1, it is characterised in that：The temperature of the Twin screw extruder It is 140-170 DEG C.
3. the preparation method of AES resins according to claim 1, it is characterised in that：The main frame of the Twin screw extruder Rotating speed is 80rpm.
4. the preparation method of AES resins according to claim 1, it is characterised in that：The temperature of the injection machine is 33- 190℃。
5. the preparation method of AES resins according to claim 1, it is characterised in that：The injection pressure of the injection machine is 60bar。
6. the preparation method of AES resins according to claim 1, it is characterised in that：The cool time of the injection machine is 5s。
CN201611156731.0A 2016-12-15 2016-12-15 Preparation method for AES resin Pending CN106696115A (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
CN201611156731.0A CN106696115A (en) 2016-12-15 2016-12-15 Preparation method for AES resin

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107599255A (en) * 2017-08-31 2018-01-19 无锡南理工科技发展有限公司 The vulcanization manufacture of glue sample and the method for inspection
CN107722486A (en) * 2017-09-19 2018-02-23 广东圆融新材料有限公司 A kind of weather-proof antibacterial and mouldproof AES materials and preparation method thereof
CN110964269A (en) * 2019-12-02 2020-04-07 天津金发新材料有限公司 Low-temperature-resistant, permanent antistatic and heat-resistant AES composition as well as preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107599255A (en) * 2017-08-31 2018-01-19 无锡南理工科技发展有限公司 The vulcanization manufacture of glue sample and the method for inspection
CN107722486A (en) * 2017-09-19 2018-02-23 广东圆融新材料有限公司 A kind of weather-proof antibacterial and mouldproof AES materials and preparation method thereof
CN110964269A (en) * 2019-12-02 2020-04-07 天津金发新材料有限公司 Low-temperature-resistant, permanent antistatic and heat-resistant AES composition as well as preparation method and application thereof

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Application publication date: 20170524